BR112018008575B1 - Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound, their use, composition for controlling harmful phytopathogenic fungi, their use and their production process, and method for controlling harmful phytopathogenic fungi - Google Patents

Abstract

ACTIVE COMPOUND COMBINATIONS COMPRISING A (THIO)CARBOXAMIDE DERIVATIVE AND A FUNGICIDAL COMPOUND. The present invention relates to active compound combinations, in particular, in a fungicidal composition, which comprises (A) a derivative of N-cyclopropyl-N-[substituted benzyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1H-pyrazole-4-carboxamide or thiocarboxamide and at least one additional fungicide active compound (B) consisting of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl] 3 ,4-dihydropyrimidin-2(1H)-one, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1- yl)butan-2-ol, (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent -3-namide or (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3- dimethylpent-3-enamide.

Description

[0001] The present invention relates to active compound combinations, in particular, in a fungicidal composition, which comprises (A) a derivative of N-cyclopropyl-N-[substituted benzyl]-3-(difluoromethyl)-5- fluoro-1-methyl-1H-pyrazole-4-carboxamide or thiocarboxamide and at least one additional fungicide active compound (B) consisting of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl) sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2, 4-triazol-1-yl)butan-2-ol, (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino) -N,3-dimethylpent-3-enamide or (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino )-N,3-dimethylpent-3-enamide. Furthermore, the invention relates to a method of curatively or preventively controlling or eradicating phytopathogenic fungi of plants or crops, the use of a combination according to the invention for treating seed, a method of protecting a seed and , not least to the treated seed.

[0002] N-cyclopropyl-N-[substituted benzyl]-carboxamides or thiocarboxamides, their preparation from commercially available materials and their use as fungicides are disclosed in WO2007/087906 , WO2009/016220 and WO2010/130767 .

[0003] N-cyclopropyl-N-[substituted benzyl]-carboxamides or thiocarboxamides in mixtures with fungicides are disclosed in WO2012/143125 and WO2015/055707. However, synergistic active compound combinations of the present invention are neither disclosed nor suggested.

[0004] The compound 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one (also called 5-fluoro-4 -imino-3-methyl-1-(p-tolylsulfonyl)pyrimidin-2-one), its fungicidal activity in soil or in mixtures with fungicides and the process for preparing it are disclosed in WO2015/103142, WO2015/103259, WO2015/103261 and WO2015/103262. The compound 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol (also known under the ISO name ipfentrifluconazole), its fungicidal activity in soil or in mixtures with fungicides and the process for preparing it are disclosed in WO 2013/007767, WO 2014/108286, WO 2016/005211, WO 2016008740, WO2015197393, WO2014095994 and WO 2014095932 . The compound (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-dimethylpent-3- enamide, its fungicidal activity and the process for preparing it are disclosed in WO2013/092224

[0005] The compound (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3- dimethylpent-3-enamide, its fungicidal activity and the process for preparing it are disclosed in WO2014/202421.

[0006] However, synergistic combinations of active compound of the present invention are neither disclosed nor suggested.

[0007] Since the environmental and economic requirements imposed on current crop protection compositions are continuously growing, in relation to, for example, the spectrum of action, toxicity, selectivity, application rate, residue formation and preparation ability favorable, and since, in addition, there can be problems, for example with resistances, a constant task is to develop new compositions, in particular fungicidal agents, which, in some areas, at least help to satisfy the requirements mentioned above .

[0008] The present invention provides active compound compositions/combinations that, in some aspects, at least achieve the defined objective.

[0009] It was surprisingly found that the combinations according to the invention not only result in the further improvement of the spectrum of action in relation to the phytopathogen to be controlled which was expected at first, but also obtain a synergistic effect extending the range of action of the component (A) and component (B) in two ways. First, the application rates of component (A) and component (B) are decreased while the action remains equally good. Second, the combination still achieves a high degree of plant pathogen control even when the two individual compounds become totally ineffective in such a low application rate range. This allows, on the other hand, a substantial expansion of the spectrum of phytopathogens that can be controlled and, on the other hand, increased safety in use.

[0010] In addition to the synergistic fungicidal activity, the active compound combinations according to the invention have additional surprising properties which, in a broader sense, can also be called synergistic, such as, for example: broadening the spectrum of activity for other phytopathogens , for example, for resistant strains of plant diseases; lower application rates of active compounds; sufficient pest control with the aid of the active compound combinations according to the invention even at application rates where the individual compounds show no or practically no activity; advantageous behavior during formulation or during use, for example during milling, sieving, emulsifying, dissolving or dispensing; improved storage stability and light stability; advantageous residue formation; improved toxicological or ecotoxicological behavior; improved plant properties, e.g. better growth, increased crop yields, a better developed root system, a larger leaf area, greener leaves, stronger shoots, fewer seeds needed, less phytotoxicity, mobilization of the plant's defense system, good plant compatibility. Therefore, the use of the active compound combinations or compositions according to the invention contributes considerably to maintaining the young cereal stand, which increases, for example, the winter survival of the treated cereal seed, and also confers quality and yield. Furthermore, the active compound combinations according to the invention can contribute to marked systemic action. Even if the individual compounds of the combination do not have sufficient systemic properties, the active compound combinations according to the invention may still have this property. Similarly, the active compound combinations according to the invention can result in a greater persistence of the fungicidal action.

em que T representa um oxigênio ou um átomo de enxofre e X é selecionado dentro da lista de 2-isopropila, 2-ciclopropila, 2-terc-butila, 5- cloro-2-etila, 5-cloro-2-isopropila, 2-etil-5-fluoro, 5-fluoro-2-isopropila, 2-ciclopropil-5-fluoro, 2-ciclopentil-5-fluoro, 2-fluoro-6-isopropila, 2-etil- 5-metila, 2-isopropil-5-metila, 2-ciclopropil-5-metila, 2-terc-butil-5- metila, 5-cloro-2-(trifluorometil), 5-metil-2-(trifluorometil), 2-cloro-6- (trifluorometil), 3-cloro-2-fluoro-6-(trifluorometil) e 2-etil-4,5-dimetila, ou um sal agroquimicamente aceitável dos mesmos, e (B) pelo menos um composto ativo fungicida adicional B que consiste em 5-fluoro-4-imino-3-metil-1-[(4-metilfenil)sulfonil]-3,4-di- hidropirimidin-2(1H)-ona, 2-[4-(4-clorofenoxi)-2-(trifluorometil)fenil]-3- metil-1-(1H-1,2,4-triazol-1-il)butan-2-ol, (2E,3Z)-5-{[1-(4-clorofenil)-1H- pirazol-3-il]oxi}-2-(metoxi-imino)-N,3-dimetilpent-3-enamida ou (2E,3Z)- 5-{[1-(4-cloro-2-fluorofenil)-1H-pirazol-3-il]oxi}-2-(metoxi-imino)-N,3- dimetilpent-3-enamida.[0011] Accordingly, the present invention provides a combination comprising: (A) at least one derivative of Formula (I)

wherein T represents an oxygen or a sulfur atom and X is selected from the list of 2-isopropyl, 2-cyclopropyl, 2-tert-butyl, 5-chloro-2-ethyl, 5-chloro-2-isopropyl, 2 -ethyl-5-fluoro, 5-fluoro-2-isopropyl, 2-cyclopropyl-5-fluoro, 2-cyclopentyl-5-fluoro, 2-fluoro-6-isopropyl, 2-ethyl-5-methyl, 2-isopropyl -5-methyl, 2-cyclopropyl-5-methyl, 2-tert-butyl-5-methyl, 5-chloro-2-(trifluoromethyl), 5-methyl-2-(trifluoromethyl), 2-chloro-6-( trifluoromethyl), 3-chloro-2-fluoro-6-(trifluoromethyl) and 2-ethyl-4,5-dimethyl, or an agrochemically acceptable salt thereof, and (B) at least one additional fungicidal active compound B consisting of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, 2-[4-(4-chlorophenoxy)-2 -(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (2E,3Z)-5-{[1-(4-chlorophenyl )-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide or (2E,3Z)-5-{[1-(4-chloro-2- fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-d imethylpent-3-enamide.

[0012] In a particular embodiment, T represents an oxygen atom.

[0013] In a particular embodiment, compound A of Formula (I) is selected from the group consisting of: N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1- methyl-1H-pyrazole-4-carboxamide (compound A1), N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A2 ), N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A3), N-(5-chloro-2 -ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A4), N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl- 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A5), N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5- fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A6), N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H- pyrazole-4-carboxamide (compound A7), N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro- 1-methyl-1H-pyrazole-4-carboxamide (compound A8), N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole- 4-carboxamide (compound A9), N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide (compound A10), N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A11), N-cyclopropyl-3-(difluoromethyl )-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide (compound A12), N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)- 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A13), N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)- 5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A14), N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1H-pyrazole-4-carboxamide (compound A15), N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H- pyrazole -4-carboxamide (compound A16), N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide ( compound A17), N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A18). N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (compound A19), and N-cyclopropyl-3 -(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothio-amide (compound A20). In a particular embodiment, component (B) is 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one. In another particular embodiment, component (B) is 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl )butan-2-ol (the ISO name is ipfentrifluconazole).

[0014] In another particular embodiment, component (B) is (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino) -N,3-dimethylpent-3-enamide.

2-[4-(4-clorofenoxi)-2-(trifluorometil)fenil]-3-metil-1-(1H- 1,2,4-triazol-1-il)butan-2-ol (o nome ISO é ipfentrifluconazol) é um composto da Fórmula

(2E,3Z)-5-{[1-(4-clorofenil)-1H-pirazol-3-il]oxi}-2-(metoxi- imino)-N,3-dimetilpent-3-enamida é um composto da Fórmula

(2E,3Z)-5-{[1-(4-cloro-2-fluorofenil)-1H-pirazol-3-il]oxi}-2- (metoxi-imino)-N,3-dimetilpent-3-enamida é um composto da Fórmula

[0015] In another particular embodiment, component (B) is (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-( methoxyimino)-N,3-dimethylpent-3-enamide. 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one (also called 5-fluoro-4-imino-3- methyl-1-(p-tolylsulfonyl)pyrimidin-2-one) is a compound of the Formula

2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol (the ISO name is ipfentrifluconazole) is a compound of Formula

(2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide is a compound of Formula

(2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-dimethylpent-3-enamide is a compound of the formula

[0016] All of the indicated mixing partners of the compound combinations of the invention may, if their functional groups make this possible, optionally form salts with suitable bases or acids.

[0017] In a particular embodiment, this invention is directed to a mixture comprising a compound A selected from compound A1, compound A2, compound A3, compound A4, compound A5, compound A6, compound A7, compound A8, compound A9, compound A10, compound A11, compound A12, compound A13, compound A14, compound A15, compound A16, compound A17, compound A18, compound A19, and compound A20, and a compound B consisting of 5-fluoro-4-imino-3-methyl -1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl- 1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy }-2-(methoxyimino)-N,3-dimethylpent-3-enamide or (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl] oxy}-2-(methoxy-imino)-N,3-dimethylpent-3-enamide.

[0018] In a particular embodiment, compound A is compound A5.

[0019] In a particular embodiment, the invention is directed to a mixture comprising a compound A which is compound A5 and a compound B which is 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl )sulfonyl]-3,4-dihydropyrimidin-2(1H)-one or 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2 ,4-triazol-1-yl)butan-2-ol.

[0020] In another particular embodiment, the invention is directed to a mixture comprising a compound A which is compound A5 and a compound B which is 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl )sulfonyl]-3,4-dihydropyrimidin-2(1H)-one.

[0021] In another particular embodiment, the invention is directed to a mixture comprising a compound A which is compound A5 and a compound B which is 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]- 3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol.

[0022] In another particular embodiment, the invention is directed to a mixture comprising a compound A which is compound A5 and a compound B which is (2E,3Z)-5-{[1-(4-chlorophenyl)-1H -pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-dimethylpent-3-enamide.

[0023] In another particular embodiment, the invention is directed to a mixture comprising a compound A which is compound A5 and a compound B which is (2E,3Z)-5-{[1-(4-chloro-2- fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide.

[0024] The invention is also directed to a mixture comprising a compound A which is compound A5 and a compound B which is ipconazole.

[0025] If the active compounds in the active compound combinations according to the invention are present in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of active compounds in active compound combinations can be varied over a relatively wide range.

[0026] In the combinations according to the invention, compounds (A) and (B) are present in a synergistically effective weight ratio of A:B in a range of 1000:1 to 1:1000, preferably in a ratio of weight of 100:1 to 1:100, more preferably in a weight ratio of 50:1 to 1:50, even more preferably in a weight ratio of 20:1 to 1:20. Further A:B ratios that can be used in accordance with the present invention with increasing preference in the order given are: 95:1 to 1:95, 90:1 to 1:90, 85:1 to 1:85, 80: 1 to 1:80, 75:1 to 1:75, 70:1 to 1:70, 65:1 to 1:65, 60:1 to 1:60, 55:1 to 1:55, 45:1 to 1:45, 40:1 to 1:40, 35:1 to 1:35, 30:1 to 1:30, 25:1 to 1:25, 15:1 to 1:15, 10:1 to 1: 10, 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2.

[0027] In a particular embodiment, the invention is directed to a mixture comprising a compound A which is N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1- methyl-1H-pyrazole-4-carboxamide and a compound B which is 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H) -one, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, ( 2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-dimethylpent-3-enamide or (2E,3Z )-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-dimethylpent-3-enamide in a ratio of weight A:B from 100:1 to 1:100, preferably from 50:1 to 1:50, more preferably from 20:1 to 1:20, even more preferably from 10:1 to 1:10, 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3.

[0028] In a particular embodiment, the invention is directed to a mixture comprising a compound A which is N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1- methyl-1H-pyrazole-4-carboxamide and a compound B which is 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H) -one, in an A:B weight ratio of from 1000:1 to 1:1000, preferably from 200:1 to 1:200, more preferably from 100:1 to 1:100, even more preferably from 20:1 to 1 :200, 10:1 to 1:100, 10:1 to 1:30, 1:1 to 1:10, 1:1 to 1:3.

[0029] In a particular embodiment, the invention is directed to a mixture comprising a compound A which is N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1- methyl-1H-pyrazole-4-carboxamide and a compound B which is 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazole -1-yl)butan-2-ol in an A:B weight ratio of from 1000:1 to 1:1000, preferably from 200:1 to 1:200, more preferably from 100:1 to 1:100, even more preferably from 20:1 to 1:200, 10:1 to 1:100, 1:1 to 1:10.

[0030] When a compound (A) or a compound (B) may be present in tautomeric form, such compound is understood above and below to also include, where applicable, corresponding tautomeric forms, even when these are not specifically mentioned. in each case.

[0031] Compounds (A) or compounds (B) that have at least one basic center are capable of forming, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid , sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids such as substituted, e.g. halosubstituted, unsubstituted C1-C4-alkanecarboxylic acids, e.g. acetic acid , saturated or unsaturated dicarboxylic acids, e.g. oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid and phthalic acid, hydroxycarboxylic acids, e.g. ascorbic acid, lactic acid, malic acid, tartaric acid and citric acid or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted C1-C4-alkane- or arylsulfonic acids, for example halosubstituted, for example methane- or p-toluenesulfonic acid. Compounds (A) or compounds (B) having at least one acidic group are capable of forming, for example, salts with bases, for example metal salts, such as alkali metal or alkaline earth metal salts, for example salts of sodium, potassium or magnesium, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl -propyl amine, or a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine. Furthermore, corresponding internal salts may optionally be formed. In the context of the invention, preference is given to agrochemically advantageous salts. In view of the close relationship between compounds (A) or compounds (B) in free form and in the form of their salts, above or below in this document, any reference to free compounds (A) or free compounds (B) or to their salts shall be understood to include also the corresponding salts or the free compounds (A) or free compounds (B), respectively, where appropriate and convenient. The equivalent also applies to tautomers of compounds (A) or compounds (B) and their salts.

[0032] In accordance with the invention, the term "combination" represents various combinations of compounds (A) and (B), for example, in a single "ready-to-mix" form, in a combined spray mixture composed of formulations separate from the single active compounds, as a “tank mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a very short period, such as a few hours or days. Preferably, the order of application of compounds (A) and (B) is not essential for working the present invention.

[0033] In one embodiment of the invention, the expression "a combination of compounds" means "composition", whereby the application of compounds (A) and (B) may be made simultaneously or consecutively, provided that the compounds (A) and (B) are present at the same time in order to exhibit a combined or synergistic effect.

[0034] The present invention further relates to compositions for combating/controlling undesirable microorganisms which comprise the active compound combinations according to the invention. Preferably, the compositions are fungicidal compositions which comprise agriculturally suitable auxiliaries, solvents, carriers, surfactants or extenders.

[0035] Furthermore, the invention relates to a method for combating unwanted microorganisms, characterized in that the active compound combinations according to the invention are applied to phytopathogenic fungi and/or their habitat.

[0036] According to the invention, the carrier is to be understood as meaning a natural or synthetic, organic or inorganic substance that is mixed or combined with the active compounds for better applicability, in particular, for application to plants or plant parts or seeds. The carrier, which can be solid or liquid, is generally inert and must be suitable for use in agriculture.

[0037] Suitable solid or liquid carriers are: for example, ammonium salts and crushed natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and crushed synthetic minerals such as finely ground silica. split, natural or synthetic alumina and silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral oils and vegetable oils, and also derivatives thereof. It is also possible to use mixtures of such carriers. Suitable solid carriers for granules are: for example crushed and fractionated natural minerals such as calcite, marble, pumice, sepiolite, dolomite, and also synthetic granules of inorganic and organic bran and also granules of organic material such as sawdust, coconut husks, corn cobs and tobacco stalks.

[0038] Suitable liquefied gaseous extenders or carriers are liquids that are gaseous at room temperature and under atmospheric pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide.

[0039] Tack enhancers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules and latex such as gum arabic, polyvinyl alcohol, polyvinyl acetate, or also natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives, mineral and vegetable oils and waxes, optionally modified.

[0040] If the extender used is water, it is also possible, for example, to use organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatic compounds such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, vegetable and mineral oils, alcohols, such as butanol or glycol, and also ethers and esters thereof, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and also water.

[0041] The compositions according to the invention may comprise other additional components, such as, for example, surfactants. Suitable surfactants are emulsifiers, dispersants or wetting agents that have ionic or non-ionic properties, or mixtures of these surfactants. Examples of these are salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of compounds containing sulfates, sulfonates and phosphates. The presence of a surfactant is necessary if one of the active compounds and/or one of the inert carriers is insoluble in water and when the application is carried out in water. The proportion of surfactants is between 5 and 40 percent by weight of the composition according to the invention.

[0042] It is possible to use dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian blue, and organic dyes such as alizarin dyes, metallic phthalocyanine-based azo dyes, and trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts.

[0043] If applicable, other additional components may also be present, eg protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilisers, sequestering agents, complex formers. In general, the active compounds can be combined with any solid or liquid additive commonly used for formulation purposes.

[0044] In general, the compositions according to the invention comprise between 0.05 and 99 weight percent, 0.01 and 98 weight percent, preferably between 0.1 and 95 weight percent, so particularly preferably between 0.5 and 90 percent by weight of the active compound combination according to the invention, most particularly preferably between 10 and 70 percent by weight.

[0045] The compositions or combinations of active compound according to the invention can be used as such or, depending on their respective physical and/or chemical properties, in the form of their formulations or forms of use prepared therefrom, as aerosols , capsule suspensions, cold spray concentrates, hot spray concentrates, encapsulated granules, fine granules, flowable seed treatment concentrates, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, pastes, pesticide coated seed, suspension concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water soluble granules or tablets, water soluble and water dispersible powders for seed treatment, powders products, natural products and synthetic substances impregnated with active compound, as well as microencapsulations in polymeric substances and seed coating materials, as well as hot spray and cold spray formulations of ULV.

[0046] The mentioned formulations can be prepared in a manner known per se, for example, by mixing the active compounds or the active compound combinations with at least one additive. Suitable additives are all common formulation aids, e.g. organic solvents, extenders, solvents or thinners, solid carriers and fillers, surfactants (such as adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and tackifiers), dispersants and/or binders or fixatives, preservatives, dyes and pigments, defoamers, inorganic and organic thickeners, water repellents, if appropriate, driers and UV stabilizers, gibberellins and also water and other processing aids. Depending on the type of formulation to be prepared in each case, further processing steps, such as wet milling, dry milling or granulation, may be necessary.

[0047] The compositions according to the invention not only comprise ready-to-use compositions which can be applied with suitable apparatus to the plant or seed, but also commercial concentrates which have to be diluted with water before use.

[0048] The active compound combinations according to the invention can be present in (commercial) formulations and in the use forms prepared from these formulations as a mixture with other active compounds (known), such as insecticides, attractive agents, sterilants , bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, protective agents and semiochemicals.

[0049] The treatment according to the invention of plants and plant parts with the active compounds or compositions is carried out directly or by action of their surroundings, habitat or storage space using common treatment methods , for example by immersion, spraying, atomization, irrigation, evaporation, spraying, vaporization, diffusion, foaming, painting, spreading, water feeding (soaking), drip irrigation and, in the case of propagation material, in particular, in the case of seeds, additionally as a dry seed treatment powder, a seed treatment solution, a water-soluble powder for treating slurry, by encrustation, by coating with one or more layers, etc. It is also possible to apply the active compounds by the ultra-low volume method or to inject the active compound preparation or the active compound itself into the soil.

[0050] The invention further comprises a method for treating minds. The invention further relates to seed treated according to one of the methods described in the previous paragraph.

[0051] The compositions or active compounds according to the invention are especially suitable for treating the seed. A large part of the damage to crop plants caused by harmful organisms is caused by an infection of the seed during storage or after sowing, as well as during and after germination of the plant. This phase is particularly critical as the roots and shoots of the growing plant are particularly sensitive and even a small amount of damage can result in the death of the plant. Thus, there is great interest in protecting the seed and the germinating plant with the use of suitable compositions.

[0052] The control of phytopathogenic fungi through plant seed treatment has been known for a long time and is the subject of continuous improvement. However, seed treatment gives a series of problems that cannot always be solved in a satisfactory way. Therefore, it is desirable to develop methods to protect the seed and the germinating plant that dispense with the additional application of crop protection agents after sowing or after emergence of the plants, or that at least considerably reduce the additional application. It is additionally desirable to optimize the amount of active compound employed in such a way as to provide maximum protection for the seed and germinating plant from attack by phytopathogenic fungi, but without damaging the plant itself by the active compound employed. In particular, methods for seed treatment must also take into account the intrinsic fungicidal properties of transgenic plants in order to obtain optimal seed and germinating plant protection with a minimum of crop protection agents that are employed.

[0053] Accordingly, the present invention also relates in particular to a method for protecting seed and germinating plants against attack by phytopathogenic fungi by treating the seed with a composition according to the invention. The invention also relates to the use of the compositions according to the invention for treating seed to protect the seed and the germinating plant against phytopathogenic fungi. Furthermore, the invention relates to seed treated with a composition according to the invention for protection against phytopathogenic fungi.

[0054] Control of phytopathogenic fungi that damage plants post-emergence is accomplished primarily by treating the soil and aboveground parts of plants with crop protection compositions. Due to concerns regarding a possible impact of the crop protection composition on the environment and the health of humans and animals, efforts are being made to reduce the amount of active compounds applied.

[0055] One of the disadvantages of the present invention is that, due to the particular systemic properties of the compositions according to the invention, seed treatment with these compositions not only protects the seed itself, but also the resulting plants after emergence, against the phytopathogenic fungi. In this way, the immediate treatment of the crop at the time of sowing or soon after can be abolished.

[0056] It is also considered advantageous that the mixtures according to the invention can be used in particular also for a transgenic seed, whereby the plant growing from this seed is capable of expressing a protein which acts against pests. By treating such a seed with the active compound combinations or compositions according to the invention, even by expression of, for example, insecticidal protein, certain pests can be controlled. Surprisingly, an additional synergistic effect can be observed in the present document, which further increases the effectiveness of protection against pest attacks.

[0057] The compositions according to the invention are suitable for protecting the seed of any plant variety employed in agriculture, in the greenhouse, in forests or in horticulture or viticulture. In particular, this takes the form of cereal seed (such as wheat, barley, rye, triticale, millet, oats), maize (maize), cotton, soybeans, rice, potatoes, sunflowers, beans, coffee, beets (e.g. sugar beet and fodder beet), peanuts, oilseed rape, poppies, olives, coconuts, cocoa, sugar cane, tobacco, vegetables (such as tomatoes, cucumbers, onions and lettuce), lawn and ornamental plants (see also below). Seed treatment of cereals (such as wheat, barley, rye, triticale and oats), maize (corn) and rice is of particular importance.

[0058] According to the invention, all plants and plant parts can be treated. By plants we mean all plants and plant populations, such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not they may be protected by the rights of plant or plant variety breeders). Cultivars and plant varieties can be plants obtained by conventional methods of propagation and improvement that can be aided or supplemented by one or more biotechnological methods, such as the use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods. By plant parts, we mean all above-ground and below-ground parts and plant organs such as bud, leaf, flower and root, e.g. leaves, needles, stems, twigs, flowers, fruiting bodies, fruit and seed, as well as roots, bulbs and rhizomes are listed. Crops and vegetative and generative propagation material, eg cuttings, bulbs, rhizomes, stolons and seeds, also belong to plant parts.

[0059] Among the plants that can be protected by the method according to the invention, one can mention major field crops such as corn, soybeans, cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (eg mustard) and Brassica carinata, rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, linseed, vines and various fruits and vegetables from various botanical taxa , such as Rosaceae sp. (e.g. seed fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (eg banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (eg lemons, oranges and grapefruit); Solanaceae sp. (e.g. tomatoes, potatoes, peppers, eggplant), Liliaceae sp., Compositiae sp. (eg lettuce, artichoke and chicory - including chicory root, endive or common chicory), Umbelliferae sp. (e.g. carrots, parsley, celery and celery), Cucurbitaceae sp. (eg cucumber - including pickled cucumber, squash, watermelon, gourds and melons), Alliaceae sp. (eg onions and leeks), Cruciferae sp. (e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radish, horseradish, watercress, Chinese cabbage), Leguminosae sp. (eg peanuts, peas and beans - such as climbing beans and fava beans), Chenopodiaceae sp. (eg mangold, chard, spinach, beetroot), Malvaceae (eg okra), Asparagaceae (eg asparagus); Graminaae sp. (eg maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (eg sunflowers), Brassicaceae sp. (e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radish and oilseed rape, mustard, horseradish and watercress), Fabacae sp. (e.g. beans, peas, peanuts), Papilionaceae sp. (eg soybeans), horticultural and forestry crops; ornamental plants; as well as genetically modified counterparts of these crops.

[0060] Wild plant species and plant cultivars, or those obtained by conventional biological breeding methods such as protoplastic fusion or crossbreeding, and parts thereof, can be treated by the methods disclosed above. Transgenic plants and plant cultivars obtained by means of genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof may be treated by the methods disclosed above. Preferably, plants of plant cultivars that are commercially available or in use are treated in accordance with the invention. Plant cultivars are understood as plants that have new properties ("traits") and were obtained by conventional breeding, mutagenesis or recombinant DNA techniques. They can be cultivars, varieties, biotypes or genotypes.

[0061] The disclosed methods can be used in the treatment of genetically modified organisms (GMOs), for example, plants or seeds. Genetically modified plants (or transgenic plants) are plants from which a heterologous gene has been stably integrated into the genome. The term “heterologous gene” essentially refers to a gene that is provided or made available outside the plant and, when introduced into the nuclear, chloroplastic, or mitochondrial genome, confers on the transformed plant new or improved agronomic or other properties by expressing a protein or polymorphic protein. - peptide of interest or down-regulating or silencing another gene (or genes) that is present in the plant (using, for example, antisense technology, co-suppression technology, RNA interference technology - RNAi or microRNA technology - miRNA) . A heterologous gene that is located in the genome is also termed as a transgene. A transgene that is defined by its particular location in the plant genome is called a transgenic or transformation event.

[0062] Plants and plant cultivars that can be treated by the methods disclosed above include all plants that have genetic material that confer particularly advantageous useful treatments to those plants (if obtained by breeding and/or biotechnological means).

[0063] Plants and plant cultivars that can be treated by the methods disclosed above include plants and plant cultivars that are resistant to one or more biotic stresses, i.e., said ones show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.

[0064] Plants and plant cultivars that can be treated by the methods disclosed above include those plants that are resistant to one or more abiotic stresses. Abiotic stress conditions can include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited nutrient availability of nitrogen, limited availability of phosphorus nutrients, shade avoidance.

[0065] Plants and plant cultivars that can be treated by the methods disclosed above include those plants characterized by improved yield characteristics. The increased yield in said plants can be the result, for example, of improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, improved carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield may be affected, in addition, by improved plant architecture (under stress and non-stress conditions), including, but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, number and distance of internodes, root growth, seed size, fruit size, pod size, number of pods or ears, number of seeds per pod or ear, seed mass, improved seed filling, reduced seed dispersal, reduced pod dehiscence and resistance to lodging. Other yield traits include seed composition, such as carbohydrate content and composition, e.g. cotton or starch, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability.

[0066] Plants and plant cultivars that can be treated by the methods disclosed above include plants and plant cultivars that are hybrid plants that already express the characteristic of heterosis or hybrid vigor that results, in general, in yield, vigor, health and superior resistance to biotic and abiotic stresses).

[0067] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars that are herbicide tolerant plants, i.e., plants rendered tolerant to one or more more certain herbicides. Such plants can be obtained by genetic transformation, or by selecting plants that contain a mutation that confers such herbicide tolerance.

[0068] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars that are insect resistant transgenic plants, i.e. plants made resistant to attack by certain addressed insects. Such plants can be obtained by genetic transformation or by selection of plants that contain a mutation that confers such insect resistance.

[0069] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars that are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation or by selection of plants that contain a mutation that confers such resistance to stress.

[0070] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars that show altered quantity, quality and/or storage stability of the harvested product and /or altered properties of specific ingredients of the harvested product.

[0071] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation or by selection as plants contain a mutation that confers such altered fiber characteristics.

[0072] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars, such as oilseed rape or related Brassica plants, with profile characteristics of changed oil. Such plants can be obtained by genetic transformation or by selection as plants contain a mutation that confers such altered oil profile characteristics.

[0073] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars, such as oilseed rape or related Brassica plants, with degrain characteristics of altered seed. Such plants may be obtained by genetic transformation or by selection of plants that contain a mutation that confers such altered seed weaning characteristics and include plants such as oilseed rape plants with delayed or reduced seed weaning.

[0074] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars, such as tobacco plants, with altered post-translational protein modification patterns .

[0075] In the context of the present invention, the active compound combinations or compositions according to the invention are applied alone or in a suitable formulation to the seed. Preferably, the seed is treated in a state where it is sufficiently stable that the treatment does not cause any harm. In general, seed treatment can take place at any time between harvest and sowing. Usually, the seed used is separated from the plant and free of cobs, husks, stems, coatings, hairs or fruit pulp. It is then possible to use, for example, seed that has been harvested, cleaned and dried to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seed which, after drying, has been treated with, for example, water and then dried again.

[0076] During seed treatment, care should be taken, in general, with the amount of the composition according to the invention applied to the seed and/or the amount of other additives is chosen in such a way that seed germination does not is adversely affected or that the resulting plant is not damaged. This must be taken into account, in particular, in the case of active compounds that may have phytotoxic effects at certain application rates.

[0077] The compositions according to the invention can be applied directly, that is, without comprising additional components and without having been diluted. In general, it is preferred to apply the compositions to the seed in the form of a suitable formulation. Suitable formulations and methods for treating seed are known to the person skilled in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1 , WO 2002/080675 A1 , WO 2002/028186 A2 .

[0078] The active compound combinations that can be used in accordance with the invention can be converted into common seed film formulations such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating materials, and also ULV formulations.

[0079] These formulations are prepared in a known manner by mixing the active compounds or combinations of the active compound with common additives, such as common extenders and also solvents or thinners, dyes, wetting agents, dispersants, emulsifiers. , defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water as well.

[0080] Suitable dyes which may be present in seed film formulations which may be used in accordance with the invention include all dyes common for such purposes. Use can be made of both pigments, which are poorly soluble in water, and dyes, which are soluble in water. Examples which may be mentioned include the dyes known under the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.

[0081] Suitable wetting agents that may be present in seed film formulations that can be used in accordance with the invention include all substances that promote moisture and are common in the formulation of agrochemical active substances. Preferably, it is possible to use alkylnaphthalenesulfonates, such as diisopropyl- or diisobutylnaphthalenesulfonates.

[0082] Suitable dispersants and/or emulsifiers that may be present in seed film formulations that can be used in accordance with the invention include all non-ionic, anionic and cationic dispersants that are common in the formulation of agrochemical active substances. . Preferably, it is possible to use nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Particularly suitable nonionic dispersants include ethylene oxide/propylene oxide blocking polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives. Particularly suitable anionic dispersants are lignosulfonates, polyacrylic salts and arylsulfonate-formaldehyde condensates.

[0083] Defoamers which may be present in seed film formulations to be used in accordance with the invention include all foam inhibiting compounds which are common in the formulation of agrochemically active compounds. Preference is given to the use of silicone defoamers, magnesium stearate, silicone emulsions, long chain alcohols, fatty acids and their salts and also organofluor compounds and mixtures thereof.

[0084] Preservatives which may be present in seed film formulations to be used in accordance with the invention include all compounds which may be used for such purposes in agrochemical compositions. By way of example, mention may be made of dichlorophen and hemiformal of benzyl alcohol.

[0085] Secondary thickeners which may be present in the seed film formulations to be used in accordance with the invention include all compounds which may be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, polysaccharides such as xanthan gum or Veegum, modified clays, phyllosilicates such as attapulgite and bentonite, and also finely divided silicic acids.

[0086] Suitable adhesives which may be present in seed film formulations to be used in accordance with the invention include all common binders which may be used in seed film coatings. Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned as preferred.

[0087] Suitable gibberellins which may be present in the seed film formulations to be used in accordance with the invention are preferably gibberellins A1, A3 (=gibberellic acid), A4 and A7; particular preference is given to the use of gibberellic acid. Gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- and Schadlingsbekampfungsmittel" [Chemistry of Crop Protection Agents and Pesticides], Volume 2, Springer Verlag, 1970, pages 401-412).

[0088] The seed film formulations that can be used in accordance with the invention can be used directly or after dilution with water prior to treating a seed of any type within a wide range. Seed film coating formulations that can be used in accordance with the invention or diluted preparations thereof can also be used to film the seed of transgenic plants. In this context, synergistic effects can also arise in interaction with substances formed by expression.

[0089] Mixing equipment suitable for treating seed with the seed film formulations that can be used in accordance with the invention or preparations prepared therefrom by adding water includes all mixing equipment that can be commonly used for filming. The specific procedure adopted during filming comprises introducing the seed into a mixer, adding the particular desired amount of seed filming formulation, as such or after pre-dilution with water, and carrying out mixing until the formulation is uniformly distributed in the seed. Optionally, a drying operation takes place.

[0090] The active compounds or compositions according to the invention have a strong microbicidal activity and can be used to control unwanted microorganisms such as fungi and bacteria, in culture protection or in material protection.

[0091] In crop protection, fungicides can be used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

[0092] In crop protection, bactericides can be used to control Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

[0093] The fungicidal compositions according to the invention can be used for the curative or protective control of phytopathogenic fungi. Accordingly, the invention also relates to curative and protective methods for controlling phytopathogenic fungi using the active compound combinations or compositions according to the invention, which are applied to the seed, plant or plant parts, fruit or soil in which the plants are grown. Preference is given to application to the plant or parts of the plant, to the fruits or to the soil in which the plants are grown.

[0094] The compositions according to the invention for combating phytopathogenic fungi in crop protection comprise an active but non-phytotoxic amount of the compounds according to the invention. "Active but non-phytotoxic amount" shall mean an amount of the composition according to the invention which is sufficient to control or completely exterminate the plant disease caused by fungi, provided that such amount, at the same time, does not inhibit notable symptoms of phytotoxicity. . These application rates can generally be varied over a wider range, such rate depending on several factors, for example, the phytopathogenic fungi, the plant or crop, climatic conditions and the ingredients of the composition according to the invention. .

[0095] The fact that the active compounds, in the concentrations necessary for the control of plant diseases, are well tolerated by plants allows the treatment of aerial plant parts, vegetative propagation material and seed, and the soil.

[0096] According to the invention, it is possible to treat all plants and plant parts. Plants are to be understood herein to mean all plants and plant populations, such as wild plants or desired or undesired crop plants (including naturally occurring crop plants). Crop plants can be plants that can be obtained through conventional breeding and optimization methods or through biotechnological and genetic engineering methods or combinations of these methods, including transgenic plants and including plant cultivars that are subject to protection or not. for plant variety protection rights. Plant parts should be understood as all above-ground and below-ground parts and organs of plants, such as bud, leaf, flower and root, in which examples that can be mentioned are leaves, tips, stems, trunks, flowers, bodies fruits, fruits and seeds and also roots, tubers and rhizomes. Plant parts also include harvested material and material from generative or vegetative propagation, eg seedlings, tubers, rhizomes, cuttings and seeds. Preference is given to the treatment of plants and the above-ground and below-ground parts and organs of the plants, such as bud, leaf, flower and root, examples that may be mentioned are leaves, tips, stems, trunks, flowers and fruits.

[0097] The active compounds of the invention, in combination with good plant tolerance and toxicity favorable to warm-blooded animals and being well tolerated by the environment, are suitable for protecting plants and plant organs, for increasing crop yields, for improving the quality of the material collected. They can preferably be used as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development.

[0098] As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as protoplastic fusion or crossbreeding, and parts thereof, are treated. In an additional preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and parts thereof are treated. The terms “parts” and “plant parts” have been explained above. Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated in accordance with the invention. Plant cultivars should be understood as plants with new properties ("traits") that were obtained by conventional breeding, mutagenesis or recombinant DNA techniques. They can be cultivars, biotypes or genotypes.

[0099] In material protection, the substances of the invention can be used for the protection of technical materials against infestation and destruction by fungi and/or undesirable microorganisms.

[00100] Technical materials are understood, in the present context, as non-living materials that have been prepared for use in engineering. For example, technical materials that must be protected from microbiological alteration or destruction by the active materials of the invention may be adhesives, glues, paper and cardboard, fabrics, rugs, leather, wood, paint and plastics, cooling lubricants and other materials that may be infested or destroyed by microorganisms. Within the context of materials to be protected are also parts of production plants and buildings, e.g. cooling circuits, heating and cooling systems, air conditioning and ventilation systems, which can be adversely affected by the spread of fungi and /or microorganisms. Within the context of the present invention, adhesives, glues, paper and cardboard, leather, wood, paints, cooling lubricants and heat exchanger liquids are preferably mentioned as technical materials, with wood being particularly preferred. Combinations according to the invention can prevent disadvantageous effects such as decay, fading and discoloration or staining. The active compound combinations and compositions according to the invention can likewise be employed to protect against colonization of objects, in particular ship hulls, sieves, nets, buildings, wharves and signaling facilities, which are in contact with sea water or brackish water.

[00101] The treatment method according to the invention can also be used in the field of protecting storage products against attack by fungi and microorganisms. In accordance with the present invention, the term "storage products" is understood to denote natural substances of plant or animal origin and their processed forms which have been obtained from the natural life cycle and for which long-term protection is required. desired. Storage products of plant origin, such as plants or parts thereof, e.g. stems, leaves, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, ground , crushed, pressed or roasted. Also under the definition of storage products is wood, either in the form of raw wood, such as construction lumber, electricity poles, and barriers, or in the form of finished articles, such as furniture or objects made of wood. Storage products of animal origin are tanned hides, leather, skins, fur and the like. The combinations according to the present invention can prevent disadvantageous effects such as decay, discoloration or staining. Preferably, the term “storage products” is understood to denote natural substances of plant origin and their processed forms, more preferably, fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms. .

[00102] Some fungal disease pathogens that can be treated according to the invention may be mentioned by way of example, but not by way of limitation:

[00103] Diseases caused by powdery mildew pathogens, such as Blumeria species, such as Blumeria graminis; Podosphaera species, such as Podosphaera leucotricha; Sphaerotheca species, such as Sphaerotheca fuliginea; Uncinula species, such as Uncinula necator;

[00104] Diseases caused by rust disease pathogens, eg Gymnosporangium species, eg Gymnosporangium sabinae; Hemileia species, such as Hemileia vastatrix; Phakopsora species such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, such as Puccinia recondita or Puccinia triticina; Uromyces species, such as, for example, Uromyces appendiculatus;

[00105] Diseases caused by pathogens of the Oomycetes group, such as, for example, species of Bremia, such as, for example, Bremia lactucae; Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Phytophthora species, such as, for example, Phytophthora infestans; Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, such as Pythium ultimum;

[00106] Leaf spot diseases and leaf wilt diseases caused, for example, by Alternaria species, such as, for example, Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporium species, such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, synonym: Helminthosporium); Colletotrichum species, such as Colletotrichum lindemuthanium; Cycloconium species, such as Cycloconium oleaginum; Diaporthe species, such as Diaporthe citri; Elsinoe species, such as Elsinoe fawcettii; Gloeosporium species, such as Gloeosporium laeticolor; Glomerella species, such as Glomerella cingulata; Guignardia species, such as Guignardia bidwelli; Leptosphaeria species, such as Leptosphaeria maculans; species of Magnaporthe, such as, for example, Magnaporthe grisea; Microdochium species, such as Microdochium nivale; Mycosphaerella species, such as, for example, Mycosphaerella graminicola and M. fijiensis; Phaeosphaeria species, such as Phaeosphaeria nodorum; Pyrenophora species, such as Pyrenophora teres; species of Ramularia, such as, for example, Ramularia collo-cygni; Rhynchosporium species, such as Rhynchosporium secalis; Septoria species, such as Septoria apii; Typhula species, such as Typhula incarnata; Venturia species, such as Venturia inaequalis;

[00107] Root and trunk diseases caused, for example, by Corticium species, such as, for example, Corticium graminearum; Fusarium species, such as Fusarium oxisporum; species of Gaeumannomyces, such as, for example, Gaeumannomyces graminis; Rhizoctonia species such as, for example, Rhizoctonia solani; Tapesia species, such as Tapesia acuformis; Thielaviopsis species, such as Thielaviopsis basicola;

[00108] Ear and panicle diseases (which include maize ears) caused, for example, by Alternaria species, such as, for example, Alternaria spp.; Aspergillus species, such as, for example, Aspergillus flavus; Cladosporium species, such as, for example, Cladosporium cladosporioides; Claviceps species, such as Claviceps purpurea; Fusarium species, such as Fusarium culmorum; Gibberella species, such as, for example, Gibberella zeae; Monographella species, such as, for example, Monographella nivalis; Septoria species, such as Septoria nodorum;

[00109] Diseases caused by soot fungi, such as, for example, Sphacelotheca species, such as, for example, Sphacelotheca reiliana; Tilletia species, such as Tilletia caries; T. controversial; Urocystis species, such as Urocystis occulta; species of Ustilago, such as Ustilago nuda; U. nuda tritici;

[00110] Fruit rot caused, for example, by Aspergillus species, such as, for example, Aspergillus flavus; Botrytis species, such as Botrytis cinerea; Penicillium species, such as Penicillium expansum and P. purpurogenum; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum; Verticilium species, such as Verticilium alboatrum;

[00111] Seed and soil-transmitted wilt and rot diseases, and also seedling diseases, caused, for example, by Fusarium species, for example, Fusarium culmorum; Phytophthora species, such as, for example, Phytophthora cactorum; Pythium species, such as Pythium ultimum; Rhizoctonia species, such as Rhizoctonia solani; Sclerotium species, such as, for example, Sclerotium rolfsii;

[00112] Cancerous diseases, galls and witches' broom caused, for example, by Nectria species, such as, for example, Nectria galligena;

[00113] Wilt diseases caused, for example, by Monilinia species, such as, for example, Monilinia laxa;

[00114] Deformations of leaves, flowers and fruits caused, for example, by species of Taphrina, for example, Taphrina deformans;

[00115] Degenerative diseases of wood plants caused, for example, by species of Esca, such as, for example, Phaemoniella clamydospora and Phaeoacremonium aleophilum and Fomitiporia mediterranea;

[00116] Flower and seed diseases caused, for example, by Botrytis species, such as, for example, Botrytis cinerea;

[00117] Plant tuber diseases caused, for example, by species of Rhizoctonia, such as, for example, Rhizoctonia solani; Helminthosporium species, such as Helminthosporium solani;

[00118] Diseases caused by bacteriopathogens, such as, for example, Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species, such as Pseudomonas syringae pv. lachrymans; Erwinia species, such as Erwinia amylovora.

[00119] Preference is given to the control of the following soybean diseases:

[00120] Fungal diseases on leaves, stems, pods and seeds caused, for example, by leaf spot of alternaria (Alternaria spec. atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cresta- leaf blight of cercospora (Cercospora kikuchii), leaf dryness by choanephora (Choanephora infundibulifera trispora (Syn.)), leaf spot by dactuliophora (Dactuliophora glycines), downy mildew (Peronospora manshurica), dryness by drechslera (Drechslera glycini), -frog (Cercospora sojina), leptosphaerulina (Leptosphaerulina trifolii) leaf spot, phyllostica (Phyllosticta sojaecola) leaf spot, pod and stem (Phomopsis soyae), powdery mildew (Microsphaera diffusa), pyrenochaeta (Pyrenochaeta glycines) leaf spot ), blight caused by rhizoctonia aerial, foliage and blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi Phakopsora meibomiae), scab (Sphaceloma glycines), re leaf drying by stem phylium (Stemphylium botryosum), target spot (Corynespora cassiicola).

[00121] Fungal diseases on roots and stem base caused, for example, by black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), dryness or wilt by fusarium, root rot and pod and collar rot (Fusarium oxisporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), root rot by mycoleptodiscus (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem dryness (Diaporthe phaseolorum), stem canker (Dia - porthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot , stem necrosis, and damp-off (Rhizoctonia solani), stem necrosis caused by sclerotinia (Sclerotinia sclerotiorum), sclerotium wilt (Sclerotinia rolfsii), root rot caused by thielaviopsis (Thielaviopsis basicola).

[00122] It is also possible to control resistant strains of the organisms mentioned above.

[00123] Microorganisms capable of degrading or altering industrial materials that can be mentioned are, for example, bacteria, fungi, yeast, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular molds, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime and algae organisms. Microorganisms of the following genera can be mentioned as examples: Alternaria such as Alternaria tenuis, Aspergillus such as Aspergillus niger, Chaetomium such as Chaetomium globosum, Coniophora such as Coniophora puetana, Lentinus such as Lentinus tigrinus, Penicillium such as Penicillium glaucum, Polyporus , such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, and Staphylococcus, such as Staphylococcus aureus.

[00124] Furthermore, the compounds of Formula (I) according to the invention also have very good antimycotic activity. They have a very broad spectrum of antimycotic activity, in particular against dermatophytes and yeasts, molds and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi in no way limits the mycotic spectrum that can be covered, but is for illustration only.

[00125] When applying the compounds according to the invention, the application rates can be varied over a wide range. The application rate/active compound dose generally applied in the treatment method according to the invention is generally and advantageously: • for treating part of plants, eg leaves (foliar treatment): from 0.1 to 10000 g/ ha, preferably from 10 to 1000 g/ha, more preferably from 50 to 300 g/ha; in the case of application by soaking or dripping, the dose can even be reduced, especially when using inert substrates such as rock wool or perlite; • for seed treatment: from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed, more preferably from 2.5 to 25 g per 100 kg of seed, with still more preferably, from 2.5 to 12.5 g per 100 kg of seed; • for soil treatment: from 0.1 to 10000 g/ha, preferably from 1 to 5000 g/ha.

[00126] The doses indicated herein are given as illustrative examples of the method according to the invention. A person skilled in the art will know how to adapt the application doses, namely, according to the nature of the plant or culture to be treated.

[00127] The combination according to the invention can be used to protect plants in a certain time span after treatment against pests and/or phytopathogenic fungi and/or microorganisms. The time range during which protection is carried out generally extends from 1 to 28 days, preferably 1 to 14 days, more preferably 1 to 10 days, even more preferably 1 to 7 days after treatment of the plants. with the combinations or up to 200 days after treatment of plant propagation material.

[00128] In addition, the combinations and compositions according to the invention can also be used to reduce the levels of mycotoxins in plants and in harvested plant material, and therefore in food and animal feed produced therefrom. Especially, but not exclusively, the following mycotoxins may be specified: Deoxynivalenol (DON), Nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2- Toxins, Fumonisins, Zearalenone Moniliformin, Fusarine, Diacetoxyscirpenol (DAS ), Beauvericin, Eniatin, Fusaroproliferin, Fusarenol, Ochratoxins, Patulin, Ergotalkaloids and Aflatoxins, which are caused, for example, by the following fungal diseases: Fusarium spec., such as Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F. oxisporum, F. proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides and others, but also by Aspergillus spec., Penicillium spec., Claviceps purpurea, Stachybotrys spec. and others.

[00129] The present invention further relates to a composition as defined herein which comprises at least one additional active ingredient selected from the group of insecticides, attractive agents, sterilants, bactericides, acaricides, nematicides, fungicides, regulators of growth, herbicides, fertilizers, protective agents and semiochemicals.

[00130] The present invention further relates to a method for controlling harmful phytopathogenic fungi, characterized in that an active compound combination as defined herein is applied to harmful phytopathogenic fungi and/or their habitat.

[00131] The present invention further relates to a process for producing compositions to control harmful phytopathogenic fungi, characterized in that an active compound combination as defined herein is mixed with extenders and/or surfactants.

[00132] The present invention further relates to the use of an active compound combination as defined herein for the control of harmful phytopathogenic fungi.

[00133] The present invention further relates to the use of an active compound combination as defined herein for the treatment of transgenic plants.

[00134] The present invention further relates to the use of an active compound combination as defined herein for the seed and seed treatment of transgenic plants.

[00135] The N-cyclopropyl amides of Formula (I) wherein T represents an oxygen atom, can be prepared by the condensation of a substituted N-cyclopropyl benzylamine with 3-(difluoromethyl)-5-fluoro-1-methyl chloride -1H-pyrazole-4-carbonyl according to WO-2007/087906 (process P1) and WO-2010/130767 (process P1 - step 10).

[00136] Substituted N-cyclopropyl benzylamines are known or can be prepared by known processes such as the reductive amination of a substituted aldehyde by cyclopropanamine (J. Med. Chem., 2012, 55 (1), 169-196) or by substitution nucleophilic acid of an alkyl (or aryl) substituted benzyl sulfonate or a cyclopropanamine substituted benzyl halide ( Bioorg. Med. Chem., 2006, 14, 8506-8518 and WO-2009/140769 ).

[00137] 3-(Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-carbonyl chloride can be prepared according to WO-2010/130767 (process P1 - steps 9 or 11)

[00138] The N-cyclopropyl thioamides of Formula (I) wherein T represents a sulfur atom, may be prepared by thioning an N-cyclopropyl amide of Formula (I) wherein T represents an oxygen atom, according to WO-2009/016220 (P1 process) and WO-2010/130767 (P3 process).

[00139] The following examples illustrate, in a non-limiting manner, the preparation of compounds of Formula (I) according to the invention. Preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide (compound A1)

[00140] Step A: Preparation of N-(2-isopropylbenzyl)cyclopropanamine

[00141] To a solution of 55.5 g (971 mmol) of cyclopropanamine in 900 ml of methanol, 20 g of 3 Å molecular sieves and 73 g (1.21 mol) of acetic acid are successively added. 72 g (486 mmol) of 2-isopropyl-benzaldehyde are then added dropwise and the reaction mixture is further heated for 4 hours.

[00142] The reaction mixture is then cooled to 0 °C and 45.8 g (729 mmol) of sodium cyanoborohydrate are added per portion over 10 minutes and the reaction mixture is stirred again for 3 hours at reflux. The cooled reaction mixture is filtered through the diatomaceous earth cake. The cake is washed abundantly with methanol and the methanolic extracts are concentrated under vacuum. Water is then added to the residue and the pH is adjusted to 12 with 400 ml of a 1N aqueous solution of sodium hydroxide. The water layer is extracted with ethyl acetate, washed with water (2 x 300 mL) and dried over magnesium sulfate to yield 81.6 g (88%) of N-(2-isopropylbenzyl)cyclopropanamine as a used yellow oil. as such in the next step.

[00143] The hydrochloride salt can be prepared by dissolving N-(2-isopropylbenzyl)cyclopropanamine in diethyl ether (1.4 mL/g) at 0 °C followed by adding a 2 M solution of hydrochloric acid in diethyl - ter (1.05 eq.). After stirring for 2 hours, N-(2-isopropylbenzyl)cyclopropanamine hydrochloride (1:1) is filtered, washed by diethyl ether and dried in vacuo at 40°C for 48 hours. Mp (melting point) = 149 °C

[00144] Step B: Preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide

[00145] To 40.8 g (192 mmol) of N-(2-isopropylbenzyl)cyclopropanamine in 1 l of dry tetrahydrofuran are added at room temperature, 51 ml (366 mmol) of triethylamine. A solution of 39.4 g (174 mmol) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-carbonyl chloride in 800 mL of dry tetrahydrofuran is then added. drip while keeping the temperature below 34°C. The reaction mixture is heated at reflux for 2 hours, then left overnight at room temperature. The salts are filtered and the filtrate is concentrated under vacuum to yield 78.7 g of a brown oil. Column chromatography on silica gel (750 g - n-heptane/ethyl acetate gradient) gives 53 g (71% yield) of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N- (2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide as a yellow oil which slowly crystallizes. Mp = 76-79°C.

[00146] Likewise, compounds A2 to A19 can be prepared according to the preparation described for compound A1. Preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide (compound A20)

[00147] A solution of 14.6 g (65 mmol) of phosphorus pentasulfide and 48 g (131 mmol) of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1- methyl-1H-pyrazole-4-carboxamide in 500 ml of dioxane are heated to 100 °C for 2 hours. 50 ml of water are then added and the reaction mixture is further heated at 100 °C for another hour. The cooled reaction mixture is filtered through a basic alumina cartridge. The cartridge is washed with dichloromethane and the combined organic extracts are dried over magnesium sulfate and concentrated under vacuum to yield 55.3 g of an orange oil. The residue is triturated with a few ml of diethyl ether until crystallization occurs. The crystals are filtered and dried under vacuum at 40°C for 15 hours to give 46.8 g (88% yield) of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)- 1-methyl-1H-pyrazole-4-carbothioamide. Mp = 64-70°C.

[00148] Table 1 provides the logP and NMR (1H) data of compounds A1 to A20.

[00149] In table 1, logP values were determined according to EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) in a reversed phase column (C 18), using the method Described below:

[00150] Temperature: 40°C; Mobile phases: 0.1% aqueous formic acid and acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Preparação de 5-fluoro-4-imino-3-metil-1-[(4-metilfenil)sulfonil]-3,4-di- hidropirimidin-2(1H)-ona (também denominado 5-fluoro-4-imino-3- metil-1-(p-tolilsulfonil)pirimidin-2-ona)[00151] Calibration was performed using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of logP values by retention times using linear interpolation between two consecutive alkanes). Maximum lambda values were determined using UV spectra from 200 nm to 400 nm and peak values of chromatographic signals.

Preparation of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one (also called 5-fluoro-4-imino- 3-methyl-1-(p-tolylsulfonyl)pyrimidin-2-one)

[00152] Step A: Preparation of 5-fluoro-4-imino-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one (also called 5-fluoro-4- imino-1-(p-tolylsulfonyl)pyrimidin-2-one)

[00153] 1.76 g (8.63 mmol) of N,O-Bis(trimethylsilyl)acetamide is added at room temperature to a stirred suspension of 1.01 g (7.85 mmol) of 5-fluorocytosine in 5 mL of acetonitrile and heated at 70 °C for 45 minutes. The light yellow solution is cooled to 5 °C, 1.65 g (8.63 mmol) of 4-toluenesulfonyl chloride is added and the mixture is kept at 5 °C for 1 hour. The suspension is warmed to room temperature overnight, poured into 75 ml of cold water and stirred for 1 hour. The white precipitate is collected, washed with plenty of water and dried by suction in air to give 1.74 g (73% yield) of 5-fluoro-4-imino-1-(p-tolylsulfonyl)pyrimidin-2-one as a fine white powder.

[00154] logP 1.45

[00155] 1H NMR (400 MHz, DMSO-d6): δ ppm 2.41 (s, 3H), 7.45 (d, J=8.1 Hz, 2H), 7.89 (d, J=8 .4 Hz, 2H), 8.24 (bs, 1H), 8.28 (d, J=6.6 Hz, 1H), 8.51 (bs, 1H).

[00156] Step B: Preparation of 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one (also called 5- fluoro-4-imino-3-methyl-1-(p-tolylsulfonyl)pyrimidin-2-one)

[00157] To a golden yellow suspension of 490 mg (1.62 mmol) of 5-fluoro-4-imino-1-(p-tolylsulfonyl)pyrimidin-2-one and 1.05 g (3.24 mmol) of cesium carbonate in 3.2 ml of N,N-dimethylformamide was added 696 mg (4.85 mmol) of iodomethane. The resulting orange suspension is stirred at 40 °C for 4 hours. The reaction mixture is then cooled to room temperature, diluted with 40 ml of ethyl acetate and washed with 40 ml of water. The aqueous phase is extracted with ethyl acetate (3 X 30 ml), the combined yellow organic phases are dried over magnesium sulfate and the volatiles are removed. The orange oil obtained is purified by column chromatography on silica (12 g - cyclohexane/ethyl acetate gradient) to give 49.2 mg (9% yield) of 5-fluoro-4-imino-3-methyl- 1-(p-tolylsulfonyl)pyrimidin-2-one as a white solid.

[00158] logP 1.26

[00159] 1H NMR (400 MHz, DMSO-d6): δ ppm 2.43 (s, 3H), 3.12 (s, 3H), 7.48 (d, J=8.1 Hz, 2H), 7.92 (d, J=8.4 Hz, 2H), 8.01 (d, J=6.0 Hz, 1H), 8.65 (bs, 1H). 2-[4-(4-Chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol is an international standard called ipfentrifluconazole (ISO nomenclature), for which specifications, references and technical explanations, including how to produce it, are published and are readily available and understandable to a person skilled in the art. Preparation of (2E,3Z)-5-{[1 -(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-dimethylpent-3 -enamide and (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3- enamide

[00160] A solution of compound (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-3- Methyl methylpent-3-enoate (1.40 g) in MeNH 2 (30~40% in EtOH, 20.00 mL) was stirred at 20 °C for 5 hours. TLC (Petroleum Ether: Ethyl Acetate=1:1, Rf=0.4) showed the reaction was complete. The mixture was concentrated and purified by preparative (neutral) HPLC to yield (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-( methoxyimino)-N,3-dimethylpent-3-enamide (540.0 mg, 1.4 mmol, 13.0% yield) as a white solid.

[00161] 1H NMR: 400 MHz DMSO

[00162] δ 8.12 (d, J=4.4 Hz, 1H), 8.00 (br, 1H), 7.74-7.67 (m, 1H), 7.67-7 .65 (d, J=9.6, 1H), 7.39-7.37 (d, J=8.4Hz, 1H), 6.02-5.97 (m, 1H), 5.82-5.97 (m, 1H), 4.43-4.41 (d, J=6.2Hz, 2H), 3.88 (s, 3H), 2.69 - 2 .68 (d, J=4.4, 3H), 1.81 (s, 3H).

[00163] MS: M+H+ =381.1

[00164] The starting material (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-3- Methyl pent-3-enoate can be prepared according to methods described in WO2013/092224 and WO2014/202421.

[00165] Likewise, (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy-imino)-N,3-dimethylpent- 3-enamide can be prepared from (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-3-methylpent- Methyl 3-enoate according to the preparation described for (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxy- imino)-N,3-dimethylpent-3-enamide.

[00166] The advanced fungicidal activity of the active compound combinations according to the invention is clear from the example below. Although the individual active compounds exhibit weakness with respect to fungicidal activity, the combinations have an activity that exceeds a simple addition of activities.

[00167] A synergistic effect of fungicides is always present when the fungicidal activity of the active compound combinations exceeds the total activities of the active compounds when applied individually. The expected activity for a given combination of two active compounds can be calculated as follows (see Colby, S.R., "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22):

[00168] If X is the effectiveness when active compound A is applied at an application rate of m ppm (or g/ha), Y is the effectiveness when active compound B is applied at an application rate of n ppm ( or g/ha), E is the effectiveness when active compounds A and B are applied at application rates of men ppm (or g/ha), respectively, and then,

[00169] The degree of effectiveness expressed in % is denoted. 0 % means an efficacy that matches that of the control while an efficacy of 100 % means that no disease is observed.

[00170] If the actual fungicidal activity exceeds the calculated value, then the combination activity is superadditive, ie there is a synergistic effect. In this case, the effectiveness that was actually observed must be greater than the value for the expected effectiveness (E) calculated from the Formula mentioned above.

[00171] An additional way of demonstrating a synergistic effect is the Tammes method (see “Isoboles, a graphic representation of synergism in pesticides”, in Neth. J. Plant Path., 1964, 70, 73-80).

[00172] The invention is illustrated by the following example. However, the invention is not limited to the example.

Example A: In vivo preventive Septoria tritici test (wheat) Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[00173] To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active compound is mixed with defined amounts of solvent and emulsifier, and the concentrate is diluted with water at the desired concentration.

[00174] To test for preventive activity, young plants are sprayed with the active compound preparation or active compound combination at the defined application rate.

[00175] After the spray coating has dried, the plants are sprayed with a spore suspension of Septoria tritici. The plants remain for 48 hours in an incubation cabin at approximately 20°C and a relative atmospheric humidity of approximately 100% and then for 60 hours at approximately 15°C in a translucent incubator at atmospheric relative humidity. of approximately 100%.

[00176] The plants are placed in the greenhouse at a temperature of approximately 15°C and a relative atmospheric humidity of approximately 80%.

[00177] The test is evaluated 21 days after inoculation. 0% means an efficacy that matches that of the untreated control while an efficacy of 100% means that no disease is observed.

* encontrado = atividade encontrada ** calc. = atividade calculada com o uso da Fórmula de Colby[00178] The table below clearly shows that the observed activity of the active compound combination according to the invention is greater than the calculated activity, i.e. a synergistic effect is present. Table A: In vivo preventive Septoria tritici test (wheat)

* found = activity found ** calc. = activity calculated using Colby's Formula

Example B: Puccinia triticin in vivo preventive test (wheat)

[00179] Solvent: 49 parts by weight of N,N-dimethylacetamide

[00180] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[00181] To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active compound is mixed with defined amounts of solvent and emulsifier, and the concentrate is diluted with water at the desired concentration.

[00182] To test for preventive activity, young plants are sprayed with the active compound preparation or active compound combination at the defined application rate.

[00183] After the spray coating has dried, the plants are sprayed with a spore suspension of Puccinia triticina. The plants remain for 48 hours in an incubation cabin at approximately 20 °C and a relative atmospheric humidity of approximately 100 %.

[00184] The plants are placed in the greenhouse at a temperature of approximately 20°C and a relative atmospheric humidity of approximately 80%.

[00185] The test is evaluated 8 days after inoculation. 0% means an efficacy that matches that of the untreated control while an efficacy of 100% means that no disease is observed.

* encontrado = atividade encontrada ** calc. = atividade calculada com o uso da Fórmula de Colby Tabela B2: teste de Puccinia triticina preventivo in vivo (trigo)

* encontrado = atividade encontrada ** calc. = atividade calculada com o uso da Fórmula de Colby[00186] The table below clearly shows that the observed activity of the active compound combination according to the invention is greater than the calculated activity, i.e. a synergistic effect is present. Table B1: in vivo preventive Puccinia triticin test (wheat)

* found = activity found ** calc. = activity calculated using Colby's Formula Table B2: Puccinia triticina preventive test in vivo (wheat)

* found = activity found ** calc. = activity calculated using Colby's Formula

Example C: In vivo preventive Blumeria test (barley)

[00187] Solvent: 49 parts by weight of N,N-dimethylacetamide

[00188] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[00189] To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active compound is mixed with defined amounts of solvent and emulsifier, and the concentrate is diluted with water at the desired concentration.

[00190] To test for preventive activity, young plants are sprayed with the active compound preparation or active compound combination at the defined application rate. After the spray coating has dried, the plants are sprayed with spores of Blumeria graminis f.sp. horde.

[00191] The plants are placed in the greenhouse at a temperature of approximately 18 °C and a relative atmospheric humidity of approximately 80 % to promote the development of mildew pustule.

* encontrado = atividade encontrada ** calc. = atividade calculada com o uso da Fórmula de Colby[00192] The test is evaluated 7 days after inoculation. 0% means an efficacy that matches that of the untreated control while an efficacy of 100% means that no disease is observed. The table below clearly shows that the observed activity of the active compound combination according to the invention is greater than the calculated activity, i.e. a synergistic effect is present. Table C: In vivo preventive Blumeria test (barley)

* found = activity found ** calc. = activity calculated using Colby's Formula

Example D: In vivo preventive Pyrenophora teres test (barley)

[00193] Solvent: 49 parts by weight of N,N-dimethylacetamide

[00194] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[00195] To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active compound is mixed with defined amounts of solvent and emulsifier, and the concentrate is diluted with water at the desired concentration.

[00196] To test for preventive activity, young plants are sprayed with the active compound preparation or active compound combination at the defined application rate.

[00197] After the spray coating has dried, the plants are sprayed with a spore suspension of Pyrenophora teres. The plants remain for 48 hours in an incubation cabin at approximately 20 °C and a relative atmospheric humidity of approximately 100%. The plants are placed in the greenhouse at a temperature of approximately 20°C and a relative atmospheric humidity of approximately 80%.

* encontrado = atividade encontrada ** calc. = atividade calculada com o uso da Fórmula de Colby[00198] The test is evaluated 8 days after inoculation. 0% means an efficacy that matches that of the untreated control while an efficacy of 100% means that no disease is observed. The table below clearly shows that the observed activity of the active compound combination according to the invention is greater than the calculated activity, i.e. a synergistic effect is present. Table D: in vivo preventive Pyrenophora teres test (barley)

* found = activity found ** calc. = activity calculated using Colby's Formula

Example E: In vitro test for the calculation of effectiveness with microorganisms

[00199] Wells of 96-well microtiter plates are filled with 10 μl of a solution of the test compounds or combinations of test compound and methanol together with the emulsifying alkylaryl polyglycol ether. Subsequently, the solvent is evaporated in a hood. In the next step, in each well, 100 μl of liquid potato dextrose medium is obtained, which has been modified with an appropriate concentration of spores or mycelium suspension of the test fungus.

[00200] The resulting concentrations of the test compounds or compound combinations in the microtiter wells are such as 50, 10, 2 and 0.4 ppm. The resulting concentration of the emulsifier in all cavities is constantly 300 ppm. With the aid of a photometer, the extinction in all cavities is measured at a wavelength of 620 nm.

[00201] The microtiter plates are then transferred for 3-5 days to a shaker at 20°C and 85% relative humidity.

* encontrado = atividade encontrada ** calc. = atividade calculada com o uso da Fórmula de Colby Tabela E2: Teste in vitro de Septoria tritici'

* encontrado = atividade encontrada ** calc. = atividade calculada com o uso da Fórmula de Colby[00202] At the end of the incubation time, the growth of the test organisms is measured again photometrically at the wavelength of 620 nm. The difference between the two extinction values (obtained before and after incubation) is proportional to the growth of the test organism. 0% efficacy means that the difference between the two extinction values is equal to or even greater than that of the untreated control, 100% efficacy means that no growth of the test organism was detected. Table E1: Leptosphaeria nodorum in vitro test

* found = activity found ** calc. = activity calculated using Colby's Formula Table E2: In vitro test of Septoria tritici'

* found = activity found ** calc. = activity calculated using Colby's Formula

Claims (13)

1. Combination of active compound, characterized in that it comprises: (A) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole -4-carboxamide, or an agrochemically acceptable salt thereof, and (B) an additional fungicidal active compound B, consisting of 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3- methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol. 2. An active compound combination according to claim 1, characterized in that compounds (A) and (B) are present in an A:B weight ratio in a range of 1000:1 to 1: 1000. 3. An active compound combination according to claim 2, characterized in that compounds (A) and (B) are present in an A:B weight ratio in a range of 100:1 to 1: 100. 4. Composition to control harmful phytopathogenic fungi, characterized by the fact that it has a content of at least one active compound combination, as defined in any one of claims 1 to 3, in addition to extenders and/or surfactants. 5. Composition, according to claim 4, characterized in that it comprises at least one additional active ingredient selected from the group of insecticides, attractive agents, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, protective agents and semiochemicals. 6. Non-therapeutic method to control harmful phytopathogenic fungi, characterized in that it comprises applying an active compound combination, as defined in any one of claims 1 to 3, or a composition, as defined in claim 4 or 5 , harmful phytopathogenic fungi and/or their habitat. 7. Process for producing compositions to control harmful phytopathogenic fungi, characterized in that it comprises mixing an active compound combination, as defined in any one of claims 1 to 3, with extenders and/or surfactants. 8. Non-therapeutic use of an active compound combination, as defined in any one of claims 1 to 3, characterized in that it is for the control of harmful phytopathogenic fungi. 9. Non-therapeutic use of a composition, as defined in claim 4 or 5, characterized in that it is for the control of harmful phytopathogenic fungi. 10. Use of an active compound combination, as defined in any one of claims 1 to 3, characterized in that it is for the treatment of transgenic plants. 11. Use of a composition, as defined in claim 4 or 5, characterized in that it is for the treatment of transgenic plants. 12. Use of an active compound combination, as defined in any one of claims 1 to 3, characterized in that it is for seed and seed treatment of transgenic plants. 13. Use of a composition, as defined in claim 4 or 5, characterized in that it is for seed and seed treatment of transgenic plants.